Binder resin solution composition, coatings, inks, adhesives and primers

ABSTRACT

The present invention provides a binder resin solution composition, and a coating, ink, and adhesive containing the composition as an active ingredient, the binder resin solution composition having a solid content of 10 to 50 wt. % and comprising (a) a chlorinated polyolefin prepared by chlorinating an isotactic polypropylene polymer having a molecular weight distribution of no more than 3 and a melting point measured by a differential scanning calorimeter of 110 to 140° C. to a chlorine content of 10 to 40 wt. % and, (b) an organic solvent.

TECHNICAL FIELD

[0001] The present invention relates to a binder resin composition usedto protect or decorate products of polyolefin resins such aspolypropylene, polyethylene, ethylene-propylene copolymers, andethylene-propylene-diene copolymers. More particularly, the presentinvention relates to a binder resin solution composition that isexcellent in adhesion to sheets, films, molded articles and the likemade from the aforementioned polyolefin resins and in solventresistance; has excellent low-temperature flowability; and is used forcoatings, primers, printing inks, or adhesives.

BACKGROUND ART

[0002] Generally, polyolefin resins are relatively inexpensive and havenoteworthy properties such as chemical resistance, water resistance,heat resistance, etc., and therefore used in a wide variety ofapplications for automotive parts, electronic parts, building materials,food packaging films, and the like. However, since polyolefin resinshaving such remarkable properties are crystalline and non-polar, it isdifficult to coat or bond products made of the resins.

[0003] Weakly chlorinated polyolefins exhibiting strong adhesion topolyolefin resins have been used as binder resins to coat or bond suchlow-adhesion polyolefin resins. For example, Japanese Examined PatentPublication No. 27489/1971 proposes an isotactic polypropylenechlorinated to have a chlorine content of 20 to 40 wt. % as a printingink binder resin for polypropylene films. Japanese Examined PatentPublication Nos. 35445/1975 and 37688/1975 teach propylene-ethylenecopolymers chlorinated to 20 to 40 wt. % as binder resins for printinginks and adhesives used on polyolefins.

[0004] Moreover, Japanese Examined Patent Publication Nos. 50381/1988and 36624/1988 propose, as primers or binder resins for coatingpolyolefin molded articles, weakly chlorinated propylene-α-olefincopolymers with a chlorine content of 5 to 50 wt. % containing acarboxylic acid and/or carboxylic anhydride.

[0005] Generally, it is desirable to keep the chlorine content as smallas possible since, as the chlorine content increases, such chlorinatedpolyolefins exhibit reduced solvent resistance and adhesion topolyolefins. However, when the chlorine content is excessively low,properties of the polyolefin solution are impaired, thickening orgelating during storage, thereby resulting in significant deteriorationin coating workability during spray coating and the like. Even when thechlorine content of the chlorinated polyolefins is maintained within arange such that coating workability during spray coating and the likedoes not suffer, the chlorinated polyolefin solutions exhibit impairedflowability when stored at low-temperatures, thereby greatly limitingtheir handling properties at low temperatures such as in winter.Although it is possible to improve low-temperature flowability bykeeping the concentration of the weakly chlorinated polyolefin in thesolution low, when the concentration is excessively low, problems arisesuch as difficult pigment dispersion in solvents upon processing intoinks and coatings, increased transportation cost, etc.

[0006] To overcome such problems, Japanese Unexamined Patent PublicationNo. 306227/1994 proposes a binder resin solution, as a binder resinsolution composition with excellent low-temperature flowability, that isobtained by dissolving a weakly chlorinated polyolefin in an alicyclichydrocarbon and aromatic hydrocarbon mixed solvent.

[0007] However, the use of such a mixed solvent requires complex processin production, resulting in high cost. Moreover, for example, when themixed solvent is used as a part of the primer component for coating,upon blending with a solvent-dispersed resin, its low-temperatureflowability is impaired due to the change in chemical composition of thesolvent. Therefore, it is hardly a fundamental solution to theaforementioned problems.

DISCLOSURE OF THE INVENTION

[0008] An object of the invention is to provide a binder resin solutioncomposition for use in coatings, primers, printing inks, or adhesives,without impairing the low-temperature flowability and workability ofweakly chlorinated polyolefins, the composition having excellent solventresistance and outstanding adhesion to polyolefin products.

[0009] Other objects and characteristics of the present invention willbecome evident by the disclosure provided hereinbelow.

[0010] The inventors conducted extensive research and found that abinder resin solution composition obtained by dissolving a chlorinatedpolyolefin prepared by chlorinating an isotactic polypropylene polymerhaving a specific molecular weight distribution and melting point in anorganic solvent imparts excellent low-temperature flowability andworkability and exhibits excellent adhesion to polyolefin products andsolvent resistance. The present invention has been accomplished based onsuch findings.

[0011] In other words, the present invention provides a binder resinsolution composition, coating, ink, adhesive, and primer as describedbelow.

[0012] 1. A binder resin solution composition having a solid content of10 to 50 wt. % comprising (a) a chlorinated polyolefin prepared bychlorinating to a chlorine content of 10 to 40 wt. % an isotacticpolypropylene polymer having a molecular weight distribution of no morethan 3 and a melting point measured by a differential scanningcalorimeter of 110 to 140° C. and (b) an organic solvent.

[0013] 2. A binder resin solution composition having a solid content of10 to 50 wt. % comprising (a) a carboxyl- containing chlorinatedpolyolefin prepared by chlorinating to a chlorine content of 10 to 40wt. % an isotactic polypropylene polymer having a molecular weightdistribution of no more than 3 and a melting point measured by adifferential scanning calorimeter of 110 to 140° C. to produce achlorinated polyolefin and graft-polymerizing with the chlorinatedpolyolefin 1 to 10 wt. % of at least one unsaturated carboxylic acidmonomer selected from the group consisting of carboxylic acids andcarboxylic acid anhydrides, and (b) an organic solvent.

[0014] 3. A binder resin solution composition having a solid content of10 to 50 wt. % comprising (a) a carboxyl-containing chlorinatedpolyolefin prepared by graft-polymerizing 1 to 10 wt. % of at least oneunsaturated carboxylic acid monomer selected from the group consistingof carboxylic acids and carboxylic acid anhydrides with an isotacticpolypropylene polymer having a molecular weight distribution of no morethan 3 and a melting point measured by a differential scanningcalorimeter of 110 to 140° C. to produce a carboxyl-containingpolyolefin and chlorinating the carboxyl-containing polyolefin to achlorine content of 10 to 40 wt. %, and (b) an organic solvent.

[0015] 4. The binder resin solution composition according to any ofItems 1 to 3, wherein the isotactic polypropylene polymer is anisotactic propylene-α-olefin random copolymer.

[0016] 5. The binder resin solution composition according to any ofItems 1 to 3, wherein the isotactic polypropylene polymer is anisotactic propylene-ethylene random copolymer.

[0017] 6. The binder resin solution composition according to any ofItems 1 to 3, wherein the isotactic polypropylene polymer is anisotactic polypropylene.

[0018] 7. The binder resin solution composition according to any ofItems 1 to 6, wherein the isotactic polypropylene polymer is produced inthe presence of a metallocene catalyst.

[0019] 8. A-coating for a polyolefin film, sheet or molded article, thecoating comprising as an active ingredient the binder resin solutioncomposition according to any of Items 1 to 7.

[0020] 9. An ink for a polyolefin film, sheet or molded article, the inkcomprising as an active ingredient the binder resin solution compositionaccording to any of Items 1 to 7.

[0021] 10. An adhesive for a polyolefin film, sheet or molded article,the adhesive comprising as an active ingredient the binder resinsolution composition according to any of Items 1 to 7.

[0022] 11. A primer for coating a polyolefin resin, the primercomprising as an active ingredient the binder resin solution compositionaccording to Item 2 or 3.

[0023] Examples of the resin components for use in the binder resinsolution composition of the present invention include chlorinatedpolyolefins prepared by chlorinating isotactic polypropylene polymers;carboxyl-containing chlorinated polyolefins prepared bygraft-polymerizing unsaturated carboxylic acid monomers with chlorinatedpolyolefins prepared by chlorinating isotactic polypropylene polymers;carboxyl-containing chlorinated polyolefins prepared bygraft-polymerizing unsaturated carboxylic acid monomers with isotacticpolypropylene polymers to give carboxyl-containing polyolefins andchlorinating the carboxyl-containing polyolefins.

[0024] Examples of isotactic polypropylene polymers used as startingmaterials include isotactic propylene-α-olefin random copolymers,isotactic polypropylenes, and the like. Preferable are isotacticpropylene-α-olefin random copolymers.

[0025] Examples of α-olefins in such isotactic propylene-α-olefin randomcopolymers are those having 2, or 4 to 20 carbons, such as ethylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene,1-dodecene, 1-hexadecene, 4-methyl-1-pentene, and the like; ethylene ispreferable. Two types of α-olefins can be used in combination. Examplesof ternary random copolymers when 2 types of α-olefins are used includeisotactic propylene-ethylene-butene random copolymers. For ease ofhandling during production, 1-butene may be used in a proportion of nomore than 0.5 mol %.

[0026] The isotactic polypropylene polymers used as starting materialshave a molecular weight distribution (Mw/Mn) of 3 or less as measured bygel permeation chromatography (GPC), and preferably 1 to 2.7.

[0027] Furthermore, the isotactic polypropylene polymers used asstarting materials have a melting point (Tm) of 110 to 140° C. asmeasured by a differential scanning calorimeter, and preferably 115 to135° C. Conditions for measuring the melting point are as follows: Asample (about 5 mg) is heated from room temperature to 240° C. at a rateof 30° C./min and maintained 240° C. for 10 minutes, and temperature isthen lowered to 30° C. at a rate of 10° C./min. The melting point refersto the peak maximum temperature.

[0028] The isotactic polypropylene polymers used as starting materialspreferably have an intrinsic viscosity (q) measured in decalin at 135°C. of 0.1 to 12 dl/g, more preferably 0.3 to 10 dl/g, and especiallypreferably 0.5 to 5 dl/g.

[0029] The isotactic propylene-α-olefin random copolymer as favoredherein, when ethylene is used as the α-olefin, preferably has 85.7 to98.5 mol % (90 to 99 wt. %) of its structural units derived frompropylene, more preferably 88.5 to 97.0 mol % (92 to 98 wt. %), andespecially preferably 89.9 to 96.0 mol % (93 to 97.3 wt. %), andpreferably has 1.5 to 14.3 mol % (1 to 10 wt. %) of its structural unitsderived from ethylene, more preferably 3.0 to 11.5 mol % (2 to 8 wt. %),and especially preferably 4.0 to 10.1 mol % (2.7 to 7 wt. %).

[0030] Isotactic polypropylene polymers usable herein are preferablyproduced in the presence of a metallocene catalyst.

[0031] Metallocene catalysts herein refer to olefin-polymerizingcatalysts derived from (A) a metallocene compound and (B) anorgano-aluminum-oxy compound, and/or an ionic compound obtained from theaforementioned transition metal compound (A), containing as necessary(C) an organo-aluminum compound. Specifically, the metallocene catalystsinclude the following 4 types:

[0032] (i) A (Metallocene compound)+B (Organo-aluminum-oxy compound);

[0033] (ii) Ionic compound obtained from (A+B);

[0034] (iii) A+B+C (Organo-aluminum compound); and

[0035] (iv) Ionic compound obtained from (A+B)+C

[0036] Examples of metallocene compound (A) as used herein includetransition metal compounds represented by Formula (1) below:

MLx   (1)

[0037] In Formula (1), M represents a transition metal that belongs toGroup 4A of the periodic table. Specifically, M is zirconium, titanium,or hafnium. X represents the valency of the transition metal.

[0038] In Formula (1), L represents ligands that coordinate with thetransition metal. At least one of the ligands L has a cyclopentadienylskeleton, and the ligand having a cyclopentadienyl skeleton may besubstituted. When the number of L is 2 or more, ligands can be the sameor different. Examples of ligands having a cyclopentadienyl skeletoninclude cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl,methylpropylcyclopentadienyl, methylbutylcyclopentadienyl,methylhexylcyclopentadienyl, methylbenzylcyclopentadienyl and likealkyl- or aralkyl-substituted cyclopentadienyl groups as well asindenyl, 4,5,6,7-tetrahydroindenyl, fluorenyl, and like groups. Thesegroups may be substituted with halogen atom(s), trialkylsilyl group(s),or the like.

[0039] When the compound represented by Formula (1) has ligand(s) Lhaving 2 or more cyclopentadienyl skeletons, two of the cyclopentadienylskeletons are preferably bonded by an alkylene such as ethylene,propylene, or the like; a substituted alkylene such as isopropylidene,diphenylmethylene, or the like; a silylene; or a substituted silylenesuch as dimethylsilylene, diphenylsilylene, methylphenylsilylene, or thelike.

[0040] Examples of ligands L other than those having a cyclopentadienylskeleton include C₁₋₁₂ hydrocarbons, alkoxy groups, aryloxy groups,sulfonic acid-containing groups (—SO₃R¹: R¹ represents alkyl,halogen-substituted alkyl, aryl, or halogen- or alkyl-substituted aryl),halogens, and hydrogen.

[0041] Metallocene compound (A) represented by Formula (1) is morespecifically represented by Formula (2) below, where, for example, thevalency of the transition metal is 4:

R² _(k)R³ _(l)R⁴ _(m)R⁵ _(n)M   (2)

[0042] In Formula (2), M is a transition metal as in Formula (1); R²represents a group (ligand) having a cyclopentadienyl skeleton; R³, R⁴and R⁵ independently are groups having a cyclopentadienyl skeleton oridentical to “L” found in Formula (1) excluding those ligands having acyclopentadienyl skeleton; and k represents an integer of 1 or more, andk+l+m+n=4.

[0043] In the present invention, transition metal compounds representedby Formula (3) below can be used as metallocene compounds (A):

[0044] In Formula (3), M represents a transition metal that belongs toGroup 4A of the periodic table. Specifically, M is zirconium, titanium,or hafnium.

[0045] In Formula (3), R¹ and R² independently represent hydrogen,halogen, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated-hydrocarbon group,silicon-containing group, oxygen-containing group, sulfur-containinggroup, nitrogen-containing group, or phosphorus-containing group.Specific examples are fluorine, chlorine, bromine, iodine, and likehalogens; C₁₋₂₀ hydrocarbon groups, such as methyl, ethyl, propyl,butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl,adamantyl, and like alkyl groups, vinyl, propenyl, cyclohexenyl, andlike alkenyl groups, benzyl, phenylethyl, phenylpropyl, and likearylalkyl groups, phenyl, tolyl, dimethylphenyl, trimethylphenyl,ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl,anthracenyl, phenanthrenyl, and like aryl groups; halogenatedhydrocarbon groups wherein the aforementioned hydrocarbon groups aresubstituted with halogens; silicon-containing groups such asmethylsilyl, phenylsilyl, and like mono-hydrocarbon-substituted silyls,dimethylsilyl, diphenylsilyl, and like di-hydrocarbon-substitutedsilyls, trimethylsilyl, triethylsilyl, tripropylsilyl,tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl,methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl, and liketri-hydrocarbon-substituted silyls, trimethylsilyl ether and like silylethers of hydrocarbon-substituted silyls, trimethylsilylmethyl and likesilicon-substituted alkyls, trimethylsilylphenyl and likesilicon-substituted aryls; oxygen-containing groups such as hydroxygroups, methoxy, ethoxy, propoxy, butoxy, and like alkoxy groups,phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy, and like aryloxygroups, phenylmethoxy, phenylethoxy, and like arylalkoxy groups;sulfur-containing groups such as the aforementioned oxygen-containinggroups wherein oxygen is substituted with sulfur; nitrogen-containinggroups such as amino groups, methylamino, dimethylamino, diethylamino,dipropylamino, dibutylamino, dicyclohexylamino, and like alkylaminogroups, phenylamino, diphenylamino, ditolylamino, dinaphtylamino,methylphenylamino, and like arylamino or alkylarylamino groups;phosphorus-containing groups such as dimethylphosphino and likephosphino groups; and the like.

[0046] In Formula (3), R¹ is preferably a hydrocarbon group andespecially it is preferably a C₁-₃ hydrocarbon group, i.e., methyl,ethyl, or propyl. R² is preferably hydrogen or a hydrocarbon group, andespecially it is preferably hydrogen or a C₁₋₃ hydrocarbon group, i.e.,methyl, ethyl, or propyl.

[0047] In Formula (3), R³ , R , R⁵, and R⁶ independently representhydrogen, halogen, C₁₋₂₀ hydrocarbon group, or C₁₋₂₀ halogenatedhydrocarbon group. Among R³, R⁴, R⁵, and R⁶ two groups, including R³,are preferably alkyl groups. Moreover, it is preferable that R³ and R⁵,or R³ and R⁶, are alkyl groups. These alkyl groups may be substitutedwith halogens, silicon-containing groups or the like. Examples ofhalogens and silicon-containing groups include those substituentsdescribed in connection with R¹ and R² above.

[0048] In Formula (3), among the groups represented by R³, R⁴, R⁵ andR⁶, those groups other than alkyl groups are preferably hydrogen.Examples of C₁₋₂₀ hydrocarbon groups include methyl, ethyl, n-propyl,i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl,cyclohexyl, heptyl, octyl, nonyl, dodecyl, eicosyl, norbornyl,adamantyl, and like linear or cyclic alkyl groups; benzyl, phenylethyl,phenylpropyl, tolylmethyl, and like arylalkyl groups; and the like. Theymay contain double or triple bond(s).

[0049] In Formula (3), two groups selected from R³, R⁴, R⁵ and R⁶ may bejoined, forming a non-aromatic monocyclic ring or polycyclic ring.

[0050] In Formula (3), X¹ and X² independently represent hydrogen,halogen, C₁₋₂₀ hydrocarbon group, C₁₋₂₀ halogenated hydrocarbon group,oxygen-containing group, or sulfur-containing group. Specifically,examples thereof include halogens, C₁₋₂₀ hydrocarbon groups, C₁₋₂₀halogenated hydrocarbon groups, oxygen-containing groups, and the like,as described in regard to R¹ and R² above.

[0051] Examples of sulfur-containing groups include those described inconnection with R¹ and R² above; methyl sulfonato, trifluoromethanesulfonato, phenyl sulfonato, benzyl sulfonato, p-toluene sulfonato,trimethylbenzene sulfonato, triisobutylbenzene sulfonato,p-chlorobenzene sulfonato, pentafluorobenzene sulfonato, and likesulfonato groups; methyl sulfinato, phenyl sulfinato, benzyl sulfinato,p-toluene sulfinato, trimethylbenzene sulfinato, pentafluorobenzenesulfinato, and like sulfinato groups; etc.

[0052] In Formula (3), Y represents C₁₋₂₀ divalent hydrocarbon group,C₁₋₂₀ divalent halogenated hydrocarbon group, divalentsilicon-containing group, divalent germanium-containing group, divalenttin-containing group, —O—, —CO—, —S—, —SO—, —SO₂—, —NR⁷—, —P(R⁷)—,—P(O)(R⁷)—, —BR⁷—, or —AlR⁷— where R⁷ represents hydrogen, halogen,C₁₋₂₀ hydrocarbon group, or C₁₋₂₀ohalogenated hydrocarbon group.Specific examples include C₁₋₂₀ divalent hydrocarbon groups such asmethylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene,1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene,1,4-dicyclohexylene, and like alkylene groups, diphenyl methylene,diphenyl-1,2-ethylene, and like arylalkylene groups, and the like;halogenated hydrocarbon groups wherein the aforementioned C₁₋₂₀ divalenthydrocarbon groups are halogenated, such as chloromethylene and thelike; divalent silicon-containing groups such as methylsilylene,dimethylsilylene, diethylsilylene, di(n-propyl)silylene,di(i-propyl)silylene, di(cyclohexyl)silylene, methylphenylsilylene,diphenylsilylene, di(p-tolyl)silylene, and di(p-chlorophenyl)silylene,and like alkylsilylenes, alkylarylsilylenes, arylsilylenes,tetramethyl-1,2-disilylene, tetraphenyl-1,2-disilylene, and likealkyldisilylenes, alkylaryldisilylenes, aryldisilylenes, and the like;divalent germanium-containing groups wherein silicon in theaforementioned silicon-containing groups is substituted with germanium;divalent tin-containing groups wherein silicon in the aforementionedsilicon-containing groups is substituted with tin; and the like. R⁷ ishalogen, C₁₋₂₀ hydrocarbon group, or C₁₋₂₀ halogenated hydrocarbon groupas described in connection with R¹ and R² above.

[0053] Among the examples above, Y is preferably a divalent silicon-,germanium-, or tin-containing group, more preferably a divalentsilicon-containing group, and especially preferably alkylsilylene,alkylarylsilylene, or arylsilylene.

[0054] In Formula (3), the preferable combination of R¹ to R⁶ is that R¹is a hydrocarbon group, R³ is a C₆₋₁₆ aryl, and R², R⁴, R⁵ and R⁶ arehydrogen. In this case, X¹ and X² are preferably halogen or C₁₋₂₀hydrocarbon groups.

[0055] Preferable examples of hydrocarbon group represented by R¹ areC₁₋₄ hydrocarbon groups, e.g., methyl, ethyl, propyl, and butyl.Examples of C₆₋₁₆ aryl represented by R³ include phenyl, α-naphthyl,β-naphthyl, anthracenyl, phenanthrenyl, pyrenyl, acenaphthyl, phenalenyl(perinaphthenyl), aceanthrylenyl, etc. Among these compounds, phenyl andnaphthyl are preferable. These aryl groups may be substituted withhalogens, C₁₋₂₀ hydrocarbon groups, or C₁₋₂₀ halogenated hydrocarbongroups as described in connection with R¹.

[0056] Specific examples of metallocene compounds (A) illustratingcombinations of R¹to R⁶ arerac-dimethylsilylene-bis(4-phenyl-1-indenyl)zirconium dichloride,rac-dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,rac-dimethylsilylene-bis[2-methyl-4-(α-naphthyl)-1-indenyl]zirconiumdichloride,rac-dimethylsilylene-bis[2-methyl-4-(β-naphthyl)-1-indenyl]zirconiumdichloride,rac-dimethylsilylene-bis[2-methyl-4-(1-anthracenyl)-1-indenyl]zirconiumdichloride, etc.

[0057] Among the metallocene compounds having the structures describedabove, preferable are as follows:rac-dimethylsilylene-bis[1-(2-methyl-4-phenylindenyl)]zirconiumdichloride,rac-dimethylsilylene-bis[1-(2-ethyl-4-phenylindenyl)]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(β-naphthyl)indenyl]]zirconiumdichloride, rac-dimethylsilylene-bis[1-[2-ethyl-4-(2-methyl-1-naphthyl)indenyl]]zirconium dichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(5-acenaphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(9-anthracenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(9-phenanthrenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(o-methylphenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(m-methylphenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(p-methylphenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(2,3-dimethylphenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(2,4-dimethylphenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(2,5-dimethylphenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(2,4,6-trimethylphenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(o-chlorophenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(m-chlorophenyl)indenyl]]zirconiumdichloride, rac-dimethylsilylene-bis[1-[2-ethyl-4-(p-chlorophenyl)indenyl]]zirconium dichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(2,3-dichlorophenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(2,6-dichlorophenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(3,5-dichlorophenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(2-bromophenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(3-bromophenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(4-bromophenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(4-biphenylyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-ethyl-4-(4-trimethylsilylphenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-(2-n-propyl-4-phenylindenyl)]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-propyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-propyl-4-(β-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-propyl-4-(2-methyl-1-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-propyl-4-(5-acenaphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-propyl-4-(9-anthracenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-propyl-4-(9-phenanthrenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-propyl-4-phenylindenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-propyl-4-(α-naphthyl)indenyl]]zirconiumdichloride, rac-dimethylsilylene-bis[1-[2-i-propyl-4-(β-naphthyl)indenyl]]zirconium dichloride,rac-dimethylsilylene-bis[1-[2-i-propyl-4-(2-methyl-1-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-propyl-4-(5-acenaphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-propyl-4-(9-anthracenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-propyl-4-(9-phenanthrenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis(1-[2-s-butyl-4-phenylindenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-s-butyl-4-(α-naphthyl)indenyl]]zirconiumdichloride, rac-dimethylsilylene-bis[1-[2-s-butyl-4-(β-naphthyl)indenyl]]zirconium dichloride,rac-dimethylsilylene-bis[1-[2-s-butyl-4-(8-methyl-9-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-s-butyl-4-(5-acenaphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-s-butyl-4-(9-anthracenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-s-butyl-4-(9-phenanthrenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-pentyl-4-phenylindenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-pentyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-butyl-4-phenylindenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-butyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-butyl-4-(β-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-butyl-4-(2-methyl-1-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-butyl-4-(5-acenaphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-butyl-4-(9-anthracenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-n-butyl-4-(9-phenanthrenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-(2-i-butyl-4-phenylindenyl)]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-butyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-butyl-4-(β-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-butyl-4-(2-methyl-1-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-butyl-4-(5-acenaphthyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-butyl-4-(9-anthracenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-i-butyl-4-(9-phenanthrenyl)indenyl]]zirconiumdichloride,rac-dimethylsilylene-bis[1-(2-neopentyl-4-phenylindenyl)]zirconiumdichloride,rac-dimethylsilylene-bis[1-[2-neopentyl-4-(α-naphthyl)indenyl]]zirconiumdichloride, rac-dimethylsilylene-bis[1-(2-n-hexyl-4-phenylindenyl)]zirconium dichloride,rac-dimethylsilylene-bis[1-[2-n-hexyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-methylphenylsilylene-bis[1-(2-ethyl-4-phenylindenyl)]zirconiumdichloride,rac-methylphenylsilylene-bis[1-[2-ethyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-methylphenylsilylene-bis[1-[2-ethyl-4-(9-anthracenyl)indenyl]]zirconiumdichloride,rac-methylphenylsilylene-bis(1-[2-ethyl-4-(9-phenanthrenyl)indenyl]]zirconiumdichloride,rac-diphenylsilylene-bis[1-(2-ethyl-4-phenylindenyl)]zirconiumdichloride,rac-diphenylsilylene-bis[1-[2-ethyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-diphenylsilylene-bis[1-[2-ethyl-4-(9-anthracenyl)indenyl]]zirconiumdichloride,rac-diphenylsilylene-bis[1-[2-ethyl-4-(9-phenanthrenyl)indenyl]]zirconiumdichloride,rac-diphenylsilylene-bis[1-(2-ethyl-4-(biphenylyl)indenyl)]zirconiumdichloride, rac-methylene-bis[1-[2-ethyl-4-phenylindenyl]]zirconiumdichloride,rac-methylene-bis[1-[2-ethyl-4-(α-naphthyl)indenyl]]zirconiumdichloride, rac-ethylene-bis[1-(2-ethyl-4-phenylindenyl)]zirconiumdichloride, rac-ethylene-bis[1-[2-ethyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-ethylene-bis[1-[2-n-propyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylgermylene-bis[1-(2-ethyl-4-phenylindenyl)]zirconiumdichloride,rac-dimethylgermylene-bis[1-[2-ethyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylgermylene-bis[1-[2-n-propyl-4-(α-naphthyl)indenyl]]zirconiumdichloride,rac-dimethylstannylene-bis[1-(2-ethyl-4-phenylindenyl)]zirconiumdichloride,rac-dimethylstannylene-bis[1-[2-ethyl-4-(9-phenanthrenyl)indenyl]]zirconiumdichloride,rac-dimethylstannylene-bis[1-(2-n-propyl-4-phenylindenyl)]zirconiumdichloride, etc.

[0058] Among the metallocene catalysts used in the present invention,known aluminoxane compounds can be used as organo-aluminum-oxycompounds.

[0059] Examples of ionic compounds usable as metallocene catalysts inthe invention include triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tri n-butylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, ferroceniumtetra(pentafluorophenyl)borate, etc.

[0060] Examples of methods for polymerizing isotactic polypropylenepolymers include suspension polymerization conducted in the presence ofa hydrocarbon solvent or propylene solvent, gas-phase polymerization,and similar methods.

[0061] The chlorinated polyolefin used herein has a chlorine content of10 to 40 wt. %. When the chlorine content is lower than 10 wt. %,solubility in solvents is impaired, and good low-temperature flowabilitycannot be attained. A chlorine content exceeding 40 wt. % is notpreferable because adhesion to polyolefins and solvent resistance arecompromised. The preferable chlorine content is 20 to 30 wt. %.

[0062] The chlorine content of the carboxyl-containing chlorinatedpolyolefin graft-polymerized with an unsaturated carboxylic acid monomershould also be 10 to 40 wt. %, and preferably 20 to 30 wt. %.

[0063] Graft-polymerizing an unsaturated carboxylic acid monomer with anisotactic polypropylene polymer can be conducted according to knownmethods, e.g., a polyolefin is brought to reaction by heating it in thepresence of a radical generator to a temperature above its melting pointand fusing it (fusion method), or by dissolving a polyolefin in anorganic solvent and heating and stirring it in the presence of a radicalgenerator (solution method).

[0064] The fusion method provides the advantage of easy operation andquick reaction because a Banbury mixer, kneader, extruder, or likeequipment is used and the reaction is conducted at temperatures higherthan the melting point up to 300° C. In the solution method, it ispreferable to use toluene, xylene, or a similar aromatic solvent as areaction solvent. A reaction temperature of 100 to 180° C. and reactiontime of 1 to 5 hours causes few side reactions and provides uniformgraft polymers.

[0065] Examples of radical generators usable in the reaction includedi-tert-butyl perphthalate, tert-butyl hydroperoxide, dicumyl peroxide,benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate,methyl-ethyl-ketone peroxide, di-tert-butyl peroxide, and likeperoxides; azobisisobutyronitrile, azobisisopropionitrile, and likeazonitriles; etc.

[0066] Examples of unsaturated carboxylic acid monomers usable in thereaction include maleic acid, maleic anhydride, fumaric acid, citraconicacid, citraconic anhydride, mesaconic acid, itaconic acid, itaconicanhydride, aconitic acid, aconitic anhydride, himic anhydride, etc.

[0067] The grafting ratio of the unsaturated carboxylic acid monomer is1 to 10 wt. %. When it is less than 1 wt. %, sufficient adhesion cannotbe attained since the content of polar group in the composition becomesexcessively low. When it is more than 10 wt. %, gelation occurs duringchlorination.

[0068] A method for graft-polymerizing an unsaturated carboxylic acidmonomer with a chlorinated polyolefin produced by chlorinating anisotactic polypropylene polymer can be conducted according to thesolution method described above. The preferable reaction temperature is60 to 120° C. Excessively low temperatures are not preferable since thereaction proceeds slowly, and excessively high temperatures are also notpreferable because the chlorinated polyolefin decomposes. The graftingratio of the unsaturated carboxylic acid monomer is 1 to 10 wt. %. Whenthe grafting ratio is less than 1 wt. %, the content of polar group inthe composition becomes too small, resulting in insufficient adhesion,and a grafting ratio more than 10 wt. % results in impaired properties.Polyolefins can be readily chlorinated according to known methods. Forexample, a polyolefin resin (an isotactic polypropylene polymer, or acarboxyl-containing polyolefin produced by grafting an unsaturatedcarboxylic acid monomer with such an isotactic polypropylene polymer) isbrought to reaction by dissolving in a chlorination solvent, andinjecting chlorine gas at a temperature of 50 to 150° C., in thepresence of a catalyst or under UV irradiation, under ambient orincreased pressure.

[0069] Catalysts usable in the chlorination reaction include, forexample, tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide,benzoyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, dilaurylperoxide, tert-butyl hydroperoxide, cyclohexanone peroxide, tert-butylperoxybenzoate, cumene hydroperoxide, tert-butyl peroxyisobutylate, andsimilar peroxides; azobisisobutyronitrile, azobisisopropionitrile, andlike azonitriles; etc.

[0070] Examples of solvents for use in the chlorinating reaction includehalogenated solvents such as tetrachloroethylene, chloroform and likehalogenated hydrocarbons. Chloroform is especially preferable.

[0071] During production of the binder resin solution composition of thepresent invention, the aforementioned chlorinated polyolefins may besolidified, dried, and dissolved in an organic solvent. Alternatively,after the chlorination reaction, the chlorination solvent is removed bydistillation and replaced with the organic solvent.

[0072] The solid content of the binder resin solution composition is 10to 50 wt. %. A solid content less than 10 wt. % poses problems such asdifficult pigment dispersion when the solution composition is processedinto inks and coatings, high transportation costs, and other problems. Asolid content more than 50 wt. % is not preferable because the impairedlow-temperature flowability greatly limits handling during winter lowtemperatures. The preferable solid content is 20 to 40 wt. %.

[0073] Toluene, xylene, or a similar aromatic organic solvent ispreferable as the organic solvent used in the binder resin solutioncomposition of the invention.

[0074] A feature of the present invention is to further improveproperties of weakly chlorinated polyolefins, which have good adhesionto polyolefins. In particular, although weakly chlorinated polyolefinsby nature exhibit better adhesion to polyolefins and improved solventresistance as their chlorine content is lowered, properties of thesolutions thereof are deteriorated, resulting in thickening/gelationduring storage and impaired low-temperature flowability. Accordingly,coating workability during spray coating and the like is significantlydeteriorated and handling properties during winter low temperatures aregreatly impaired. However, a binder resin solution composition, asdisclosed herein, comprising as a resin component a weakly chlorinatedpolyolefin, obtained by chlorinating an isotactic polypropylene polymerhaving a molecular weight distribution of no more than 3 and a meltingpoint measured by a differential scanning calorimeter of 110 to 140° C.,has excellent solution quality and low-temperature flowability, as wellas excellent solvent resistance and adhesion to polyolefins.

[0075] The binder resin solution composition of the present inventioncan be used as a binder composition for a coating for polyolefin films,sheets, molded articles, and the like, as well as a binder compositionfor inks, adhesives, etc. Furthermore, such a composition containing acarboxyl-containing chlorinated polyolefin produced bygraft-polymerizing an unsaturated carboxylic acid monomer can be used asa primer for coating polyolefin bumpers.

[0076] Although the binder resin solution composition of the inventioncan be applied as a coating per se, it can also be used as a coating orink by mixing with a pigment, a solvent, or other additives. While thebinder resin provides a coating film with well-balanced properties, itcan further be used in combination with alkyd resins, acrylic resins,polyacryl polyols, polyester resins, polyester polyols, polyetherresins, polyether polyols, polyurethane resins, chlorinated polyolefins,etc., as required.

[0077] The binder resin solution composition of the invention, becauseit achieves excellent solvent resistance and adhesion to polyolefinproducts without impairing the low-temperature flowability andworkability of weakly chlorinated polyolefins, can be used as a binderresin solution composition for coatings, primers, printing inks, oradhesives.

BEST MODE FOR CARRYING OUT THE INVENTION

[0078] Examples are given below to illustrate the invention in moredetail, but the scope of the invention is not limited to these examples.

EXAMPLE 1

[0079] Polymerization was carried out over 30 minutes by introducing 900ml of hexane into a 2-liter autoclave sufficiently charged withnitrogen, adding thereto 1 mmol of triisobutylaluminum, heating to 70°C., supplying propylene and ethylene to adjust the total pressure to0.71 MPa, adding 0.30 mmol of methylaluminoxane and 0.001 mmol(calculated as a Zr atom) ofrac-dimethylsilylene-bis[1-(2-methyl-4-phenylindenyl)]zirconiumdichloride, and continuously supplying propylene and ethylene tomaintain 0.71 MPa total pressure. After polymerization and deaeration,an isotactic propylene-ethylene random copolymer was recovered in anexcess of methanol, and dried under reduced pressure for 12 hours at110° C.

[0080] The isotactic propylene-ethylene random copolymer thus obtained(hereinafter referred to as PE-1) exhibited a melt flow rate of 10 g/10min (ASTM 1238: 230° C., 2.16 kg load), ethylene content of 4.0 mol %(2.7 wt. %), Mw/Mn of 2.6, and Tm of 131° C.

[0081] PE-1 (280 g) and chloroform (2520 g) were introduced into anautoclave equipped with a stirrer. After charging with nitrogen forabout 5 minutes, the autoclave was heated to 110° C. to sufficientlyfuse the resin. Subsequently, 1.4 g of tert-butylperoxy-2-ethylhexanoatewas added and chlorine gas was injected to acquire 3 reaction solutionseach having a different chlorine content. The reaction solvent, i.e.,chloroform, was distilled off under reduced pressure, and toluene wasadded to dissolve, thereby producing toluene solutions of chlorinatedpolyolefin having a chlorine content of 15 wt. %, 20 wt. %, and 25 wt.%, respectively, and a solid content of 20 wt. % each.

EXAMPLE 2

[0082] In a similar manner to the first part of Example 1, an isotacticpropylene-ethylene random copolymer (hereinafter referred to as PE-2)was produced that exhibited a melt flow rate of 3 g/10 min (ASTM 1238:230° C., 2.16 kg load), ethylene content of 6.2 mol % (4.2 wt. %), Mw/Mnof 2.0, and Tm of 117° C.

[0083] PE-2 was chlorinated as in the latter half of Example 1 to obtaintoluene solutions of chlorinated polyolefin having a chlorine content of15 wt. %, 20 wt. %, and 25 wt. %, respectively, and a solid content of20 wt. % each.

Comparative Example 1

[0084] A polypropylene (hereinafter referred to as PP-1) produced in thepresence of a titanium catalyst was chlorinated as in Example 1 toobtain toluene solutions of chlorinated polypropylene having a chlorinecontent of 15 wt. %, 20 wt. %, and 25 wt. %, respectively, and a solidcontent of 20 wt. % each.

Comparative Example 2

[0085] A crystalline propylene-ethylene random copolymer (ethylenecontent: 4.0 mol % (2.7 wt. %); hereinafter referred to as PE-3)produced in the presence of a titanium catalyst was chlorinated as inExample 1 to obtain toluene solutions of chlorinated polyolefin having achlorine content of 15 wt. %, 20 wt. %, and 25 wt. %, respectively, anda solid content of 20 wt. % each.

Comparative Example 3

[0086] A crystalline propylene-ethylene random copolymer (ethylenecontent: 5.9 mol % (4.0 wt. %); hereinafter referred to as PE-4)produced in the presence of a titanium catalyst was chlorinated as inExample 1 to obtain toluene solutions of chlorinated polyolefin having achlorine content of 15 wt. %, 20 wt. %, and 25 wt. %, respectively, anda solid content of 20 wt. % each.

EXAMPLE 3

[0087] Graft polymerization was conducted over 5 hours by introducing280 g of PE-1, 16.8 g of maleic anhydride, 5.6 g of di-tert-butylperoxide and 420 g of toluene into an autoclave equipped with a stirrer,charging with nitrogen for about 5 minutes, and heating and stirring at140° C. After the reaction, the reaction solution was introduced into anexcess of methyl ethyl ketone to precipitate the resin. The resin thusobtained was further washed with methyl ethyl ketone several times toremove unreacted maleic anhydride. After drying under reduced pressure,the thus-obtained maleic anhydride-modified polyolefin was chlorinatedas in Example 1 to obtain toluene solutions of maleic anhydride-modifiedchlorinated polyolefin having a chlorine content of 10 wt. %, 15 wt. %,20 wt. %, and 25 wt. %, respectively, and a solid content of 20 wt. %each.

EXAMPLE 4

[0088] PE-2 was subjected to reaction according to the method describedin Example 3 to obtain toluene solutions of maleic anhydride-modifiedchlorinated polyolefin having a chlorine content of 10 wt. %, 15 wt. %,20 wt. %, and 25 wt. %, respectively, and a solid content of 20 wt. %each.

Comparative Example 4

[0089] PP-1 was brought to reaction as in Example 3 to obtain toluenesolutions of maleic anhydride-modified chlorinated polypropylene havinga chlorine content of 10 wt. %, 15 wt. %, 20 wt. %, and 25 wt. %,respectively, and a solid content of 20 wt. % each.

Comparative Example 5

[0090] PE-3 was reacted as in Example 3 to obtain toluene solutions ofmaleic anhydride-modified chlorinated polyolefin having a chlorinecontent of 10 wt. %, 15 wt. %, 20 wt. %, and 25 wt. %,.respectively, anda solid content of 20 wt. % each.

Comparative Example 6

[0091] PE-4 was subjected to reaction as in Example 3 to obtain toluenesolutions of maleic anhydride-modified chlorinated polyolefin having achlorine content of 10 wt. %, 15 wt. %, 20 wt. %, and 25 wt. %,respectively, and a solid content of 20 wt. % each.

Comparative Example 7

[0092] A syndiotactic polypropylene (trade name: CHIARO, manufactured byMitsui Chemicals, Inc.) produced in the presence of a metallocenecatalyst was brought to reaction as in Example 3 to obtain toluenesolutions of maleic anhydride-modified chlorinated polyolefin having achlorine content of 10 wt. %, 15 wt. %, 20 wt. %, and 25 wt. %,respectively, and a solid content of 20 wt. % each.

EXAMPLE 5

[0093] PE-1 was chlorinated as in Example 1 to obtain toluene solutionsof chlorinated polyolefin having a chlorine content of 10 wt. %, 15 wt.%, 20 wt. %, and 25 wt. %, respectively, and a solid content of 20 wt. %each. These toluene solutions of chlorinated polyolefin (350 g each)were introduced into three-neck flasks equipped with a stirrer, droppingfunnel, thermometer, and refluxer. Maleic anhydride (1 g) was introducedinto each flask. After heating the reaction system to 80° C. in an oilbath maintained at a specific temperature, 0.5 g of benzoyl peroxidediluted with 5 ml of toluene was added dropwise via the dropping funnelover a period of about 10 minutes. After dropwise addition, reaction wascarried out for 5 hours by stirring while maintaining the reactionsystem at 80° C. After reaction, the reaction solutions were cooled andtreated with toluene, thereby yielding toluene solutions of maleicanhydride-modified chlorinated polyolefin each having a solid content of20 wt. %.

EXAMPLE 6

[0094] PE-2 was brought to reaction as in Example 5 to obtain toluenesolutions of maleic anhydride-modified chlorinated polyolefin having achlorine content of 10 wt. %, 15 wt. %, 20 wt. %, and 25 wt. %,respectively, and a solid content of 20 wt. % each.

[0095] Chlorinated polyolefin solutions obtained in Examples 1 to 6 andComparative Examples 1 to 7 were investigated for the followingproperties:

[0096] (1) Low-Temperature Flowability

[0097] Tables 1 and 2 show a property (low-temperature flowability) ofthe chlorinated polyolefin solutions obtained in Examples 1 to 6 andComparative Examples 1 to 7 after storing each chlorinated polyolefinsolution for 10 days in the air at 5° C., −5° C., or 31 10° C., whereinA means “flowable” and B refers to “not flowable (gelated)”.

[0098] (2) Gasoline Resistance

[0099] The viscosity of the chlorinated polyolefin solutions obtained inExamples 1 to 6 and Comparative Examples 1 to 7 was adjusted by tolueneso that the drain time using a Ford cup #4 was 12 sec/20° C. Thesesolutions were spray-coated onto polypropylene boards (produced bypress-molding SB-E3 manufactured by Mitsui Chemicals, Inc., according toknown method; 100 mm×50 mm; thickness: 2 mm) washed with isopropylalcohol, and dried at 80° C. for 10 minutes. A two-component urethanecoating was further spray-coated thereon in an amount of 50 to 60 g/m²,and the boards were dried for about 10 minutes at room temperature andfor 45 minutes at 80° C. Testing was conducted on the polypropyleneboards after being left for 24 hours at room temperature. The coatedpolypropylene boards were scratched through to the underlying boardsurface, and immersed for 2 hours in conventional unleaded gasolinemaintained at 20° C., after which the condition of the coatings wasexamined. Results are shown in Tables 1 and 2.

[0100] (3) Interlaminar Adhesion

[0101] Polypropylene boards coated as in (2) above using the maleicanhydride-modified chlorinated polyolefin solutions obtained in Examples3 to 6 and Comparative Examples 4 to 7 were provided with a grid patternof hundred 1-mm squares that reach the underlying board surface. Anadhesive cellophane tape was placed on the grid, the tape was peeledperpendicular to the coated surface, and the number of squares that werenot peeled away with the tape was counted. Table 2 shows the results.

[0102] (4) Interlaminar Adhesion After Immersion in Warm Water

[0103] Polypropylene boards coated as in (2) above using the maleicanhydride-modified chlorinated polyolefin solutions obtained in Examples3 to 6 and Comparative Examples 4 to 7 were immersed in warm watermaintained at 40° C. for 240 hours and subjected to the same examinationas in (3) above. Table 2 shows the results.

[0104] (5) Gasohol Resistance

[0105] Polypropylene boards coated as in (2) above using the maleicanhydride-modified chlorinated polyolefin solutions obtained in Examples3 to 6 and Comparative Examples 4 to 7 were immersed in gasohol(conventional unleaded gasoline:ethanol=90:10 (weight ratio)) maintainedat 20° C. for 120 minutes, and the condition of the coatings wasexamined. Table 2 shows the results. TABLE 1 Low- Chlorine contenttemperature flowability Gasoline (Wt. %) 5° C. −5° C. −10° C. resistanceExample 1 15 A B B No peeling 20 A A B No peeling 25 A A A No peelingExample 2 15 A B B No peeling 20 A A B No peeling 25 A A A No peelingComparative 15 B B B No peeling Example 1 20 B B B No peeling 25 A B BPeeling Comparative 15 B B B No peeling Example 2 20 A B B No peeling 25A A B Peeling Comparative 15 B B B No peeling Example 3 20 A B B Nopeeling 25 A A B Peeling

[0106] Analysis of the Results Provided in Table 1

[0107] In Example 1, an isotactic polypropylene polymer having amolecular weight distribution of 2.6 and a redmelting point measured bya differential scanning calorimeter of 131° C. was chlorinated anddissolved in an organic solvent. In Example 2, an isotacticpolypropylene polymer having a molecular weight distribution of 2.0 anda melting point measured by a differential scanning calorimeter of 117°C. was chlorinated and dissolved in an organic solvent. In ComparativeExamples 1, 2 and 3, chlorinated polyolefins were dissolved in anorganic solvent. The solutions of Examples 1 and 2 are clearly superiorto those of Comparative Examples 1, 2 and 3 in low-temperatureflowability. Moreover, the polymers of Examples 1 and 2 are alsosuperior in gasoline resistance. TABLE 2 Interlaminar ChlorineLow-temperature adhesion after content flowability Interlaminarimmersion in Gasoline Gasohol (Wt. %) 5° C. −5° C. −10° C. adhesion warmwater resistance resistance Ex. 3 10 A B B 100 100 No peeling No peeling15 A B B 100 100 No peeling No peeling 20 A A A 100 100 No peeling Nopeeling 25 A A A 90 90 No peeling No peeling Ex. 4 10 A B B 100 100 Nopeeling No peeling 15 A B B 100 100 No peeling No peeling 20 A A A 100100 No peeling No peeling 25 A A A 95 100 No peeling No peeling Ex. 5 10A B B 100 100 No peeling No peeling 15 A B B 100 100 No peeling Nopeeling 20 A A A 100 100 No peeling No peeling 25 A A A 85 90 No peelingNo peeling Ex. 6 10 A B B 100 100 No peeling No peeling 15 A B B 100 100No peeling No peeling 20 A A A 100 100 No peeling No peeling 25 A A A 9090 No peeling No peeling Comp. 10 B B B 100 100 No peeling No peelingEx. 4 15 B B B 80 80 No peeling No peeling 20 B B B 75 75 No peeling Nopeeling 25 A A B 50 60 Peeling Peeling Comp. 10 B B B 100 100 No peelingNo peeling Ex. 5 15 B B B 100 100 No peeling No peeling 20 A B B 100 100No peeling No peeling 25 A A A 75 75 Peeling Peeling Comp. 10 B B B 100100 No peeling No peeling Ex. 6 15 B B B 100 100 No peeling No peeling20 A B B 100 100 No peeling No peeling 25 A A A 75 70 Peeling PeelingComp. 10 B B B 90 90 No peeling Peeling Ex. 7 15 A B B 75 80 PeelingPeeling 20 A A B 60 65 Peeling Peeling 25 A A A 45 40 Peeling Peeling

[0108] Analysis of the Results Provided in Table 2

[0109] In Example 3, an isotactic polypropylene polymer having amolecular weight distribution of 2.6 and a melting point measured by adifferential scanning calorimeter of 131° C. was modified by maleicanhydride and then chlorinated, followed by being dissolved in anorganic solvent. In Example 5, an isotactic polypropylene polymer asused in Example 3 was chlorinated and then modified by maleic anhydride,followed by being dissolved in an organic solvent. In Example 4, anisotactic polypropylene polymer having a molecular weight distributionof 2.0 and a melting point measured by a differential scanningcalorimeter of 117° C. was modified by maleic anhydride and thenchlorinated, followed by being dissolved in an organic solvent. InExample 6, an isotactic polypropylene polymer as used in Example 4 waschlorinated and then modified by maleic anhydride, followed by beingdissolved in an organic solvent. In Comparative Examples 4 to 7,polyolefins graft modified with maleic anhydride were chlorinated anddissolved in an organic solvent. In spite of their betterlow-temperature flowability, the polymers used in Examples 3 to 6 arealso superior to those used in Comparative Examples 4, 5 and 6 in termsof coating film properties. Furthermore, the polymers of Examples 3 to 6are superior to that of Comparative Example 7 in coating filmproperties. Therefore, the polymers of Examples 3 to 6 can be consideredas unprecedented polymers combining outstanding low-temperatureflowability and excellent coating film properties.

1. A binder resin solution composition having a solid content of 10 to50 wt. % comprising (a) a chlorinated polyolefin prepared bychlorinating to a chlorine content of 10 to 40 wt. % an isotacticpolypropylene polymer having a molecular weight distribution of no morethan 3 and a melting point measured by a differential scanningcalorimeter of 110 to 140° C. and (b) an organic solvent.
 2. A binderresin solution composition having a solid content of 10 to 50 wt. %comprising (a) a carboxyl-containing chlorinated polyolefin prepared bychlorinating to a chlorine content of 10 to 40 wt. % an isotacticpolypropylene polymer having a molecular weight distribution of no morethan 3 and a melting point measured by a differential scanningcalorimeter of 110 to 140° C. to produce a chlorinated polyolefin andgraft- polymerizing with the chlorinated polyolefin 1 to 10 wt. % of atleast one unsaturated carboxylic acid monomer selected from the groupconsisting of carboxylic acids and carboxylic acid anhydrides, and (b)an organic solvent.
 3. A binder resin solution composition having asolid content of 10 to 50 wt. % comprising (a) a carboxyl-containingchlorinated polyolefin prepared by graft-polymerizing 1 to 10 wt. % ofat least one unsaturated carboxylic acid monomer selected from the groupconsisting of carboxylic acids and carboxylic acid anhydrides with anisotactic polypropylene polymer having a molecular weight distributionof no more than 3 and a melting point measured by a differentialscanning calorimeter of 110 to 140° C. to produce a carboxyl-containingpolyolefin and chlorinating the carboxyl-containing polyolefin to achlorine content of 10 to 40 wt. %, and (b) an organic solvent. 4-11.(canceled)
 12. The binder resin solution composition according to claim1, wherein the isotactic polypropylene polymer is an isotacticpropylene-α-olefin random copolymer.
 13. The binder resin solutioncomposition according to claim 2, wherein the isotactic polypropylenepolymer is an isotactic propylene-α-olefin random copolymer.
 14. Thebinder resin solution composition according to claim 3, wherein theisotactic polypropylene polymer is an isotactic propylene-α-olefinrandom copolymer.
 15. The binder resin solution composition according toclaim 1, wherein the isotactic polypropylene polymer is an isotacticpropylene-ethylene random copolymer.
 16. The binder resin solutioncomposition according to claim 2, wherein the isotactic polypropylenepolymer is an isotactic propylene-ethylene random copolymer.
 17. Thebinder resin solution composition according to claim 3, wherein theisotactic polypropylene polymer is an isotactic propylene-ethylenerandom copolymer.
 18. The binder resin solution composition according toclaim 1, wherein the isotactic polypropylene polymer is an isotacticpolypropylene.
 19. The binder resin solution composition according toclaim 2, wherein the isotactic polypropylene polymer is an isotacticpolypropylene.
 20. The binder resin solution composition according toclaim 3, wherein the isotactic polypropylene polymer is an isotacticpolypropylene.
 21. The binder resin solution composition according toclaim 1, wherein the isotactic polypropylene polymer is produced in thepresence of a metallocene catalyst.
 22. The binder resin solutioncomposition according to claim 2, wherein the isotactic polypropylenepolymer is produced in the presence of a metallocene catalyst.
 23. Thebinder resin solution composition according to claim 3, wherein theisotactic polypropylene polymer is produced in the presence of ametallocene catalyst.
 24. A coating for a polyolefin film, sheet ormolded article, the coating comprising as an active ingredient thebinder resin solution composition according to claim
 1. 25. A coatingfor a polyolefin film, sheet or molded article, the coating comprisingas an active ingredient the binder resin solution composition accordingto claim
 2. 26. A coating for a polyolefin film, sheet or moldedarticle, the coating comprising as an active ingredient the binder resinsolution composition according to claim
 3. 27. An ink for a polyolefinfilm, sheet or molded article, the ink comprising as an activeingredient the binder resin solution composition according to claim 1.28. An ink for a polyolefin film, sheet or molded article, the inkcomprising as an active ingredient the binder resin solution compositionaccording to claim
 2. 29. An ink for a polyolefin film, sheet or moldedarticle, the ink comprising as an active ingredient the binder resinsolution composition according to claim
 3. 30. An adhesive for apolyolefin film, sheet or molded article, the adhesive comprising as anactive ingredient the binder resin solution composition according toclaim
 1. 31. An adhesive for a polyolefin film, sheet or molded article,the adhesive comprising as an active ingredient the binder resinsolution composition according to claim
 2. 32. An adhesive for apolyolefin film, sheet or molded article, the adhesive comprising as anactive ingredient the binder resin solution composition according toclaim
 3. 33. A primer for coating a polyolefin resin, the primercomprising as an active ingredient the binder resin solution compositionaccording to claim
 2. 34. A primer for coating a polyolefin resin, theprimer comprising as an active ingredient the binder resin solutioncomposition according to claim 3.